Citation: Zhangran Ye, Zhixuan Yu, Jingming Yao, Lei Deng, Yunna Guo, Hantao Cui, Chongchong Ma, Chao Tai, Liqiang Zhang, Lingyun Zhu, Peng Jia. An ionically conductive and compressible sulfochloride solid-state electrolyte for stable all-solid-state lithium-based batteries[J]. Chinese Chemical Letters, ;2025, 36(8): 110272. doi: 10.1016/j.cclet.2024.110272 shu

An ionically conductive and compressible sulfochloride solid-state electrolyte for stable all-solid-state lithium-based batteries

Zhangran Ye ^a ,
Zhixuan Yu ^a ,
Jingming Yao ^a ,
Lei Deng ^a ,
Yunna Guo ^a ,
Hantao Cui ^a ,
Chongchong Ma ^a ,
Chao Tai ^a ,
Liqiang Zhang ^{a, *,} ,
Lingyun Zhu ^{c, *,} ,
Peng Jia ^{a, b, *,}

a.
Clean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, China
b.
Hebei Key Laboratory of Applied Chemistry, College of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao 066004, China
c.
School of Materials Science and Engineering, Anhui University, Hefei 230601, China

lqzhang@ysu.edu.cn

22149@ahu.edu.cn

pengjia@ysu.edu.cn

Received Date: 1 May 2024
Revised Date: 10 July 2024
Accepted Date: 16 July 2024
Available Online: 18 July 2024

Figures(6)

Halide electrolytes, renowned for their excellent electrochemical stability and wide voltage window, exhibit significant potential in the development of high energy density solid-state batteries featuring high voltage cathode materials. In this study, we present the development and synthesis of a 0.6Li₂S-ZrCl₄ solid electrolyte, demonstrating an ion conductivity of 1.9 × 10^–3 S/cm at 25 ℃. Under a pressure of 500 MPa, the relative density of the electrolyte can reach 97.37%, showcasing its commendable compressibility. 0.6Li₂S-ZrCl₄ served as the electrolyte, and we assembled batteries utilizing a LiCoO₂ (LCO) positive electrode, Li_9.54Si_1.74P_1.44S_11.7Cl_0.3 (LSPSCl) coating, and Li-In negative electrode for laboratory testing. At 25 ℃, this all-solid-state battery demonstrated an impressive discharge capacity retention rate of 86.99% (with a final discharge specific capacity of 110.5 mAh/g) after 250 cycles at 24 mA/g and 100 MPa stack pressure. Upon substituting the positive electrode material with LiNi_0.8Mn_0.1Co_0.1O₂ (NMC811) and assembling an all-solid-state battery, it demonstrated a discharge capacity retention rate of 74.17% after 200 cycles at 3.6 mA/g and 100 MPa stack pressure in an environment at 25 ℃ (with a final discharge specific capacity of 103.3 mA/g). Our findings hold significant implications for the design of novel superionic conductors, thereby contributing to the advancement of all-solid-state battery technology.
- All-solid-state battery,
- Halide solid electrolyte,
- Sulfide substitution,
- Lithium-ion conductor,
- Solid-state ionics
1. [1]
  D.H.S. Tan, A. Banerjee, Z. Chen, et al., Nat. Nanotechnol. 15 (2020) 170–180. doi: 10.1038/s41565-020-0657-x
2. [2]
  L.Z. Fan, H.C. He, C.W. Nan, Nat. Rev. Mater. 6 (2021) 1003–1019. doi: 10.1038/s41578-021-00320-0
3. [3]
  S.X. Xia, X.S. Wu, Z.C. Zhang, et al., Chem 5 (2019) 753–785.
4. [4]
  C. Ling, T. Naren, X. Liu, et al., Mater. Today Energy 36 (2023) 101372.
5. [5]
  Y. Chen, C. Ling, K. Long, et al., Chem. Eng. J. 488 (2024) 150888.
6. [6]
  A.J. Samson, K. Hofstetter, S. Bag, et al., Energy Environ. Sci. 12 (2019) 2957–2975. doi: 10.1039/c9ee01548e
7. [7]
  R. Murugan, V. Thangadurai, W. Weppner, Angew. Chem. Int. Ed. 46 (2007) 7778. doi: 10.1002/anie.200701144
8. [8]
  V. Thangadurai, S. Narayanan, D. Pinzaru, Chem. Soc. Rev. 43 (2014) 4714–4727. doi: 10.1039/c4cs00020j
9. [9]
  J.A. Lewis, F.J.Q. Cortes, Y. Liu, et al., Nat. Mater. 20 (2021) 503–510. doi: 10.1038/s41563-020-00903-2
10. [10]
  R.H. Basappa, T. Ito, H. Yamada, J. Electrochem. Soc. 164 (2017) A666. doi: 10.1149/2.0841704jes
11. [11]
  Q.S. Dai, J.M. Yao, C.C. Du, et al., Adv. Funct. Mater. 32 (2022) 12. doi: 10.53388/aging202204012
12. [12]
  T. Kimura, A. Kato, C. Hotehama, et al., SSI 333 (2019) 45–49.
13. [13]
  S.L. Li, R.F. Song, R.A. Xu, et al., J. Alloys Compd. 968 (2023) 11.
14. [14]
  D.W. Zeng, J.M. Yao, L. Zhang, et al., Nat. Commun. 13 (2022) 13.
15. [15]
  Y. Pang, Y. Liu, J. Yang, et al., MT Nano 18 (2022) 100194.
16. [16]
  L. Long, S. Wang, M. Xiao, et al., J. Mater. Chem. A 4 (2016) 10038–10069.
17. [17]
  S. Xiao, L. Ren, W. Liu, et al., Energy Storage Mater. 63 (2023) 102970.
18. [18]
  Z. Li, J. Fu, X. Zhou, et al., Adv. Sci. 10 (2023) 2201718.
19. [19]
  X.N. Li, J.W. Liang, X.F. Yang, et al., Energy Environ. Sci. 13 (2020) 1429–1461. doi: 10.1039/c9ee03828k
20. [20]
  C.H. Wang, J.W. Liang, J. Luo, et al., Sci. Adv. 7 (2021) 9.
21. [21]
  B. He, F. Zhang, Y. Xin, et al., Nat. Rev. Chem. 7 (2023) 826–842.
22. [22]
  X. Li, J. Liang, J. Luo, et al., Energy Environ. Sci. 12 (2019) 2665–2671. doi: 10.1039/c9ee02311a
23. [23]
  X. Li, J. Liang, N. Chen, et al., Angew. Chem. 131 (2019) 16579–16584. doi: 10.1002/ange.201909805
24. [24]
  K. Kim, D. Park, H.G. Jung, et al., Chem. Mater. 33 (2021) 3669–3677. doi: 10.1021/acs.chemmater.1c00555
25. [25]
  P. Adeli, J.D. Bazak, K.H. Park, et al., Angew. Chem. Int. Ed. 58 (2019) 8681–8686. doi: 10.1002/anie.201814222
26. [26]
  S. Chen, C. Yu, S. Chen, et al., Chin. Chem. Lett. 33 (2022) 4635–4639.
27. [27]
  M. Feinauer, H. Euchner, M. Fichtner, et al., ACS Appl. Energy. Mater. 2 (2019) 7196–7203. doi: 10.1021/acsaem.9b01166
28. [28]
  L. Hu, J.Z. Wang, K. Wang, et al., Nat. Commun. 14 (2023)3807.
29. [29]
  H. Kwak, D. Han, J. Lyoo, et al., Adv. Energy. Mater. 11 (2021) 10.
30. [30]
  J. Liang, X. Li, S. Wang, et al., J. Am. Chem. Soc. 142 (2020) 7012–7022. doi: 10.1021/jacs.0c00134
31. [31]
  S. Chen, C. Yu, C. Wei, et al., Chin. Chem. Lett. 34 (2023) 107544.
32. [32]
  S. Chen, C. Yu, C. Wei, et al., Energy Mater. Adv. 4 (2023) 0019.
33. [33]
  R. Schlem, A. Banik, S. Ohno, et al., Chem. Mater. 33 (2021) 327–337. doi: 10.1021/acs.chemmater.0c04352
34. [34]
  K. Wang, Q.Y. Ren, Z.Q. Gu, et al., Nat. Commun. 12 (2021) 11. doi: 10.1007/978-3-030-53352-6_2
35. [35]
  H. Yan, R. Song, R. Xu, et al., J Energy Chem. 86 (2023) 499–509.
36. [36]
  C. Yu, Y. Li, K.R. Adair, et al., Nano Energy 77 (2020) 105097.
37. [37]
  A. Albinati, B. Willis, J. Appl. Crystallogr. 15 (1982) 361–374.
38. [38]
  Z. Xu, B. Fu, X. Hu, et al., Ceram. Int. 49 (2023) 32903–32912.
39. [39]
  Y. Xia, J. Li, J. Zhang, et al., J. Power Sources 543 (2022) 231846.
40. [40]
  F. Han, A.S. Westover, J. Yue, et al., Nat/Energy 4 (2019) 187–196. doi: 10.1038/s41560-018-0312-z
41. [41]
  F. Han, Y. Zhu, X. He, et al., Adv. Energy. Mater. 6 (2016) 1501590.
42. [42]
  P. Qing, Z. Wu, A. Wang, et al., Adv. Mater. 35 (2023) 2211203. doi: 10.1002/adma.202211203
43. [43]
  C. Wei, Y. Xiao, Z. Wu, et al., Sci. China. Chem. 67 (2024) 1990–2001. doi: 10.1007/s11426-024-2055-4
44. [44]
  Q. Luo, L. Ming, D. Zhang, et al., Energy Mater. Adv. 4 (2023) 0065.
45. [45]
  C. Wei, C. Liu, Y. Xiao, et al., Adv. Funct. Mater. 34 (2024) 2314306.
46. [46]
  T.H. Ma, Z.X. Wang, D.X. Wu, et al., Energy Environ. Sci. 16 (2023) 2142–2152. doi: 10.1039/d3ee00420a
47. [47]
  X. Li, J. Liang, X. Yang, et al., Energy Environ. Sci. 13 (2020) 1429–1461. doi: 10.1039/c9ee03828k
48. [48]
  N. Kamaya, K. Homma, Y. Yamakawa, et al., Nat. Mater. 10 (2011) 682–686. doi: 10.1038/nmat3066
49. [49]
  X. Chi, Y. Zhang, F. Hao, et al., Nat. Commun. 13 (2022) 2854.
50. [50]
  F. Bahmani, C. Rodmyre, A. Smirnova, ECS Meeting Abstracts 243, ECS, Inc., 2023, p. 1017. 10.1149/ma2023-0161017mtgabs
51. [51]
  C. Yu, F. Zhao, J. Luo, et al., Nano Energy 83 (2021) 105858.
52. [52]
  J. Gu, Z. Liang, J. Shi, et al., Adv. Energy. Mater. 13 (2023) 2203153.
53. [53]
  Y.B. Song, H. Kwak, W. Cho, et al., Curr. Opin. Solid. St. M. 26 (2022) 100977.
54. [54]
  G. Deysher, P. Ridley, S.Y. Ham, et al., Mat. Today Phys. 24 (2022) 100679.
55. [55]
  T.M. Heenan, A. Wade, C. Tan, et al., Adv. Energy Mater. 10 (2020) 2002655.
56. [56]
  W. Huang, T. Liu, L. Yu, et al., Science 384 (2024) 912–919. doi: 10.1126/science.ado1675
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